Treatment of hydrocarbons with activated magnesium silicates



Patented Oct. 19, 1948 ITED TREATMENT OF HYDROCARBONS WITH ACTIVATEDMAGNESIUM SILICATES William A. La Lands. .lr.. Upper Darby, Pa..assignor to Attapulgus Clay Company, Philadelphia, Pa a corporation ofDelaware lilo Drawing. Original application March 14. 1942, Serial No.434,776. Divided and this application August 18, 1948, Serial No.690,332

Claims.

The present invention relates to the preparation of adsorbentcompositions. and more particularly to the production of magnesiumsilicates ormixtures containing magnesium silicates suitable for use asdecolorlzing adsorbents and catalysts.

- This application is a division of my copendin application SerialNumber 434,778, illed March 14, 1942, now U. 8. Patent No. 2,434,418,dated January 18. 1948. entitled "Preparation and use of magnesiumsilicate adsorbents. An object of this invention is the preparation ofadsorbent compositions by reacting in aqueous solution an alkali metalsilicate and a water-sol.- uble salt of magnesium. in the presence of acomund yielding ammonium ions (NH4+) in aqueus solution. 3 i

A further object of this invention is the activation of magnesiumsilicate adsorbents subsequent to their formation, by treatment with acompound yielding ammonium ions (NI-14+) in aqueous solution.

It has been proposed heretofore to produce magnesium silicates byreacting an alkali metal silicate with a water-soluble salt ofmagnesium, or by reacting an alkali metal silicate with a wa- 'watertodissolve the compound, and to this solution is added a second solutioncontaining a watar-soluble ammonium saltvand a water-soluble ter-sclublecalcium salt and transposing the resuiting calcium silicate to magnesiumsilicate by treatment with a water-soluble m nesium salt. A furthermethod comprises the reatment of naturallyqoccurring calcium silicateswith a water-soluble salt of magnesium. A still further method involvesthe treatment of magnesium basic carbonate with silica. water. andalkali at elevated temperature and pressure.

However. I have discovered that by carrying outthe processesaforementioned at an elevated temperature in the presence of a compoundyielding NH4+' ions in aqueous solution. or by treating the products ofsaid processes at an elevated temsalt or magnesium. While chemicallyequivalent amounts of alkali metal silicate and water-soluble magnesiumsalt may be employed, I prefer to have present in the reaction mixture.an excess of magnesium salt over that required for complete reactionwith the alkali metal silicate. The quantity of ammonium salt-may vary.and good resuits have been obtained using amounts chemically equivalentto the water-soluble magnesium salt. The mixture is then heated,preferably at its boiling point. for a period of time suiilcient tocomplete the reaction, whereby there is produced a water-insolubleproduct comprising magnesium silicate. Silicates corresponding to thapproximate formulae MgQSiOr, MgO.2SlO2. 14803510: and 2MgO.3SiOs may beproduced. The insoluble product is then separated from the reactionmixture by suitable means, for example. by decantation, filtering orcentrifuging, and the product is then washed free of solublesalts, driedtoa suitable volatile matter content. and reduced to particles ofdesired size. As alternative procedures. the alkali metal silicate maybe reacted with a water-soluble magnesium salt to form a waterinsolublemagnesium silicate, and the latter may then be separated and treated atelevated temperature with a compound capable of yielding ammonium ionsin aqueoussolution. Or,- a magnesium silicate maybe prepared by reactingan alkali metal silicate with qa w'ater-soluble calcium perature with acompound yielding NH+ ions in aqueous solution, I am able to produceimproved adsorbents suitable for use as decolorizing agents orcatalysts. Such silicates difler from those formed in the absence ofcompounds yielding NH4+ ions. in that they possess a higher decolorizingor bleaching power for oils, a lower retentivity. and permit higherfiltration rates when employed in the decolorization of oils, wax, andthe like. Furthermore. the adsorbents precate.

salt. and the resulting insoluble calcium silicate then transposed intoa magnesium silicate by treatment with a. water-soluble magnesium salt.

Or, a magnesium basic carbonate may be treated with silica, water. andalkali at elevated temperature and pressure to produce a magnesium sili-During' the formation of the silicates, a compound capable of yieldingammonium ions may advantageously be present. or the silicates. afterformation, may be treated at elevated temperature with a water-solubleammonium salt.

- pounds at ordinary temperatures produces no improvement.

In carrying out my process, I may employ commercially available alkalimetal silicates having a ratio of NazO1SiO2 or KzOfSiOa of 1:1 to 1:4.The silicates may be used in aqueous solution of desired concentration,and the ratio of Na2O:SiO1 or KaOtSiOa may be adjusted by the additionof suitable quantities of NaOH or KOH. Commercial sodium silicate havinga ratio of NazO:SiOz of 1:322, and a Baum gravity of 41, has been foundsatisfactory for use. Alkali metal silicates produced by the treatmentof silica or other highly siliceous minerals with alkali metalhydroxides, oxides, peroxides, or carbonates. may also be used. Forexample, materials containin alkali metal silicates produced by fusingfuller's earth, bentonite, or other naturally occurring silicates, withan alkali metal carbonate, or by treating such naturally occurringsilicates with an alkali metal hydroxide solution at elevatedtemperatures, may be satisfactorily employed. As compounds capable offurnishing ammonium-ions NH4+) in aqueous solution, I may utilize forexample, ammonium chloride, ammonium sulfate, or ammonium nitrate.Insofar as the watersoluble magnesium salts are concerned, I prefer touse the chloride or the sulfate, although other soluble magnesium saltsmay be employed. Magnesium chloride solutions, particularly magnesiumchloride brines from salt wells, are available in large quantities andat relatively low cost, and may be satisfactorily employed in thepractice of my invention. While satisfactory results may be obtainedusing chemically equivalent amounts of an ammonium compound and of asoluble magnesium salt, based upon the alkali content of the alkalimetal silicate employed, it is not necessary to do so in all cases, asthe completion of the reaction may be favored by having present anexcess of the magnesium salt or the ammonium salt. The concentrations ofthe solutions employed may vary over a wide range, for example, from 1per cent up to saturation at the boiling point of the solution ormixture of solutions. The temperature at which the reaction is carriedout is preferably that which is necessary to maintain the solution ormixture of the reactants at its boiling point, however, higher or lowertemperatures may beutilized. In general. temperatures of from about 150F. to about 400 F. are suitable. sufllcient pressure being maintainedupon the reaction mixture to prevent substantial loss of watertherefrom. The reaction time will vary considerably, depending upon thequantities and concentrations of the reactants, the degree of agitationof the reaction mixture, and the temperature at which the reaction iscarried out. In

some cases the formation of the magnesium silicate may be completed in afew hours, whereas in other cases the reaction may require to hours, ormore. The magnesium silicate, upon completion of the reaction, may befreed of soluble salts by washing with water, and then dried 4 to asuitable volatile matter content (water content) prior to reduction ofthe silicate to desired particle size. Depending upon the use to whichthe metal silicate is to be put, the particle size and volatile mattercontent will vary. The volatile content may range from 10 per cent toabout 30 per cent by weight, and is preferably of the order of 15 percent-20 per cent by weight. The particle size or mesh of the silicatemay be of the order of 20-60 mesh for the percolation decolorization ofoils, or 4-60 mesh for the catalytic treatment of oils or othercompounds, or finer than 100 mesh for the contact decolorization of oilsor the catalytic conversion. of hydrocarbons.

My invention may be further illustrated by the following examples which,however, are not to be construed as limiting the scope thereof:

1. 204 parts by weight of MgCl:.6H:O and 107 parts by weight of NHCIwere dissolved in 1000 parts by weight of water, and the resultingsolution was introduced into a reaction vessel provided with a stirrerand a reflux condenser. A second solution was made up consisting of 676parts by weight of sodium silicate (lNazO: 3.228102, 41 B.) and 475parts by weight of water, and this solution was added to the solutionfirst mentioned. with vigorous stirring, The mixture was then boiled for2 hours at 214 F., the reflux condenser serving to prevent loss ofwater. As a result of the reaction between the sodium silicate and themagnesium chloride, in the presence of the ammonium chloride, there wasproduced a white, insoluble precipitate comprising magnesium silicate,which was filtered from the solution, washed free of soluble salts withwater, and air dried. The adsorbent product so produced had a volatilecontent (water) of 26.2 per cent by weight, determined by heating asample of it at 1800 F. for 20 minutes. The volume weight of the product(26.2 per cent volatile content) was 31.4 pounds per cubic foot. Thedecolorizing efficiency of this material was determined by contacting itwith a hydrocarbon lubricating oil stock having a Saybolt universalviscosity of 150 seconds at 210 R, an A. P. I. gravity of 255, and an O.D. color of 821. Upon completion of the contacting step, the adsorbentwas filtered from the oil and the color of the oil was measured. Theresults obtained with different quantitles of the adsorbent at differenttemperatures are as follows:

O. D. color Lubricating oil stock 821 Contacted with 10% of adsorbent at500 F.

for 20 minutes 272 Contacted with 15% of adsorbent at 500 F.

for 20 minutes 223 Contacted with 15% of adsorbent at 300 F.

for 20 minutes 245 2. A solution consisting of 1220 parts by weight ofsodium silica e (1NaaO:3.22SiOz, 41 B.) and 700 parts by weight of waterwas added, with vigorous agitation, to a second solution consisting of356 parts by weight of MgClz.6HzO, 562 parts by weight of NHiCl, and1020 parts by weight of water. The mixture was boiled for 2 hours at 220F., under a reflux condenser, until the reaction between the sodiumsilicate and magnesium chloride was substantially complete. Theresulting water-insoluble precipitate comprising magnesium silicate wasfiltered from the solution, washed free of soluble salts with water, andair dried. The adsorbent so produced had a volatile content (water) of20.9 per cent by weight, and a volume weight of 15.3 pounds per cubicfoot.

. ture of-about 1700 F. for ,3 hours.

The procedure above set forth was repeated. I

with the exception that the NH4C] was omitted. The resulting product,formed in the absence of NH4C1, had a volatile content (water) or 24.8per cent by weight. and a volume weight oi 27.7 pounds per, cubic foot.

The decolorizing efiici-enciesoi the two produets repared as abovedescribed were determined by contacting the adsorbents with the samelubricating oil stock as employed in Example 1. The

results obtained with diflerent quantities or the adsorbents atdiflerent temperatures are as follows:

Adsorbent prepared in the presence of NH4Cl: O. D. color Lubricating oilstock 821 Contacted with 10% of adsorbent at 500 F. for 20 minutes 272Contacted with of-adsorbent at 300 F. for minutes 208 Adsorbent preparedin the absence oi. NH4 C1: Contacted with 10% of adsorbent at 500 'F.for 20 minutes 311 contacted with 15% of adsorbent at 300 F. for 20minutes 3. 155 parts by weight of Polkville bentonite (volatile content17.2 per cent) was thoroughly admixed with 338 parts by weight of sodaash (NazCOa containing 10 per cent by weight or water). The mixture wasdried at 220 F. to remove water, and thereafter was fused at atemperature of about 1800 F. for 3 hours. The fused mass was cooled, andthen ground and screened to pass 200 mesh.

200 parts by weight of the finely divided maby weight 01' water to forma slurry. To this slurry was added a solution consisting of 533 parts byweight 01' MEClaGHiO, 283 parts by weight or NH4C1, and 2000 parts byweightoi water. The

mixture was then boiled, under a reflux condenser, for 10 hours. withvigorous itation. Upon completion of the heating per od, the finelydivided treated material comprising a mixture of waiter-insolublesilicates including magnesium silicate. was filtered from the solution.thoroughly washed with water to remove soluble salts, and then airdried. The silicate mixture so produced had a volatile content (water)or 35.0 per cent by weight. and a volume weight oi 38.3 pounds per cubicfoot. v

The procedure above set forth was repeated, with the exception that theNHsCl was omitted. The resulting silicate mix-ture hada volatile content(water) or 38.8 per cent, and a volume weight of 30.2 pounds per cubicfoot.

The decolorlzing efllciencies oi the two silicate mixtures prepared asabove described were deter mined by contacting the silicates with alubriterial from the fusion was mixed with 500 parts by weight 01 waterto form a slurry. To this slurry was added a solution consisting of 268parts by weight of MgC12.6H2O, 142 parts by weight of NH4C1, and 400parts by weight of water. The mixture was then boiled, under a refluxcondenser, for 10 hours, with vigorous agitation. Upon completion of theheating period, the finely divided treated material comprising a mixtureor waterinsoluble silicates, including magnesium silicate, wasfiltered-from the solution, thoroughly washed with water to removesoluble salts, and then air dried. The silicate mixture so produced hada volatile content (water) of 35.2 per cent by weight, and a volumeweight or 21.5 pounds per cubic .foot. The decolorizing emciency or thesilicate mixture was determined by contacting with a lubricating 011stock having an O. D. color 850.

' The results obtained with diflerent quantities or.

the silicate mixture are as follows:

. O. D. color Lubricating on stock 850 Contacted with 10% of silicate at500 F. for

20 minutes 382 Contacted with 15% B silicate at 500 F. ion

20 minutes 2'14 between the sodium silicate and the magnesium eating oilstock having an 0. D. color of 821. The results obtained with diflerentquantities of the silicate mixtures at difl'erent temperatures are asfollows:

Silicates prepared in the presence 01 NHlCl: O. D. color Lubricating oilstock 821 Contacted with 10% 01' silicate at 500 F. for 20 minutes 394Contacted with 15% of silicate at 500 F. for 20minutes Contacted with10% of silicate at 300 F. for 20 minutes 454 v Silicates prepared in theabsence or NH4C1:

Contacted with 10%;0! silicate at 500 F. for 20 minutes, 559 Contactedwith 15% of silicate at 500 F. for 20 minutes 481 Contacted with 15% ofsilicate at 300 -F. for 20 minutes 613 5. 204 parts by weight ofM8Cla6I-Ia0 was dissolved in 1000 parts by weight of water, and theresulting solutionwas introduced into a reaction vessel provided with astirrer and a reflux condenser. A second solution was made up consistingof 6'76 parts by weight oi sodium silicate (1Na2O:3.22SiO2, 41 B.) and475 parts by weight of water, and this solution was added to thesolution first mentioned, with vigorous stirring. The mixture was thenboiled for 2 hours at 214 F., the reflux condenser serving to preventloss of water. As a result of the reaction chloride, there was producedawhite,.insoluble precipitate comprising magnesium silicate, which wasfiltered from the solution. 220 parts by weight or this product wasdispersed in 1000 parts by weight of water, and a solution of parts byweight of NHlNO: in 1000 parts by weight of water was added. Themixturewas boiled for 2 hours with constant agitation, and the insolublesilicate was filtered from the solution, thoroughly washed with water.and dried.

The magnesium silicate so produced had a volatile content (water) of19.5 per cent by weight, determined by heating a sample oif'the silicateat 1800" F. for 20 minutes. The volume weight of the silicate (19.5 percent volatile content) was 31.3 pounds per cubic foot. The decolorlzingeflicienoy of the silicate was determined by 0. D. color Lubricting oilstock 821 Contacted with 15% of silicate at 500 F. for

20 minutes 210 contacted with 15% of silicate at 300 F. for

20 minutes 259 The magnesium silicate initially prepared, withoutactivation with NHsNOB, gave the following results:

0. D. color Lubricating oil stock 821 contacted with 15% of silicate at500 F. for

20 minutes 285 Contacted with 15% of silicate at 300 F. for

20 minutes 335 In order to determine the decolorizing efliciency forvegetable oil of the silicate activated with NH4NO3 and of the silicatenot activated with NH4NO3, a soda-cut linseed oil was con- .tacted witheach of the silicates at 210 F. for

15 minutes. The linseed oil was decolorized to 5.8 red (Lovibond, 6"column, 35 yellow), the

yield from the silicate not activated with NH4NO3 being arbitrarilydesignated at 100 per cent. Upon this basis, the yield of oil from thesilicate activated with NH4NO3 was found to be 225 per cent.

6. 220 partsby weight of a commercial magnesium silicate produced inaccordance with the disclosure of U. S. Patent 2,163,525 to Caldwell,was dispersed in 1000 parts by weight of water, and a solution of 160parts by weight of NHiNOa in 1000 parts by weight of water was added.The mixture was boiled for 2 hours with constant agitation, and theinsoluble silicate was filtered from the solution, thoroughlywashed withwater, and dried. The activated magnesium silicate had a volatilecontent (water) or 21.4 per cent by weight.

The decoloring emciency for vegetable oil of the commercial magnesiumsilicate aforesaid activated with NH4NO3, and the magesium silicate notactivated with NH4NO3 was determined by contacting these materials withsoda-cut linseed oil at 210 F. for 15 minutes. The linseed oil wasdecolorized to 5.8 red (Lovi'bond, 6" column, yellow), the'yield fromthe magnesium silicate not activated with NH4NO3 being arbitrarilydesignated as 100 per cent. Upon this basis, the yield of oil from themagnesium silicate activated with NH4NO3 was found to be 385 per cent.

From the above examples, it will be apparent that, in accordance withthe present invention, highly efficient decolorizing adsorbents may beprepared, and that such adsorbents are superior to those produced in theabsence of a compound yielding NH4+ ions in aqueous solution.

While, in the preparation of the adsorbents above described, I prefer toeffect reaction of the components in aqueous solution by simply boilingthe solution under a reflux condenser, I may dispense with the condenserand add water when necessary, or I may carry out the reaction undersuperatmospheric pressure, for example, in a reaction vessel atpressures up to several hundred pounds per square inch. The quantitiesand concentrations of the reaction components, as well as the reactiontemperatures, may also be varied considerably from those shown in theexamples.

The adsorbent compositions of the present invention may be employed notonly as decolorizing agents for'hyclrocarbon oils, vegetable oils,waxes, and the like, but also may be utilized as catalysts in thecracking or conversion of \hydrocarbon oils and gases into motor fuel;in the reforming of gasoline to increase the anti-knock value thereof;in the thermal treatment ofoil distillates such as gasoline, furnaceoil, and the like for the removal of gum-forming compounds and sulfurcompounds; in the hydrogenation, dehydrogenation, or cyclization ofhydrocarbon oils and gases; or as a supporter or promoter for othercatalysts such as the metals, metal oxides, metal sulfides, and thelike. In the cracking or conversion of hydrocarbon oils, the catalystsmay be employed in the form of granules or pellets for fixed bed ormoving bed operations, or in the form of a finely divided powder for the"fluid" catalyst processes.

The cracking of hydrocarbon oils such as petroleum gas oil or higherboiling oil in the presence of the silicate catalyst of the presentinvention may be carried out at temperatures between 700 F. and 1150 F.,and preferably between 850 F. and 1050 F., under atmospheric orsuperatmospheric pressure, using flow rates, for example, of from 1 to 5volumes of oil per volume of catalyst per hour.

The reforming of gasoline stocks or heavy naphthas in the presence ofthe silicate catalysts to increase the anti-knock value of the gasolineor naphtha may be performed at temperatures of the order of 900 F. to1025 F. under atmospheric or higher pressure.

The conversion of hydrocarbon gases into motor fuel by cracking andpolymerization in the presence of th silicate catalysts may beaccomplished at temperatures between 950 F. and 1150 F., and atpressures up to about 3500 lbs. per square inch, while thedehydrogenation of such gases to produce olefin hydrocarbons may beeffected at similar temperatures but preferably at atmospheric orslightly superatmospheric pressures.

The removal of gum-forming and sulfur compounds from hydrocarbondistill-ates such as gasoline, kerosine, and furnace oil may be carriedout in the presense of the silicate catalyst at temperatures of theorder of 550 F. to'750. F., preferably at substantially atmosphericpressure, although pressures up to about pounds per square inch may beemployed.

The following examples will serve to illustrate the use of the silicateadsorbents of the present invention as catalysts in the conversion ofhydrocarbon oil into motor fuel.

7. A water-insoluble magnesium silicate was prepared in accordance withthe general procedure set forth in Example 1, such silicate having avolatile content of 21.6 per cent-by weight and a particle size finerthan 200 mesh. The silicate was compressed into small pellets in aconventional pelleting machine, and the pellets were introduced into anexternally heated reaction vessel. A petroleum gas oil, having adistillation range of 282 F. to 692 F. and an A. P. I. gravity of 33.1,was vaporized and passed at substantially atmospheric pressure throughthe catalyst chamber containing the magnesium silicate pellets. Thereaction temperature was maintained at 891 1 and the new rate at 1volume of gas oil per volume 01' catalyst per hour. The products of thecracking operation were collected and separated by fractionation, andthere was obtained 31.4 per cent by volume of 400 F. end

point gasoline, and 6.2 per cent by weight of uncondensed gas. Thecracking reaction was repeated, using magnesium silicate producedaccording to the general procedure of Example 1,

- with the exception that the N'H4Cl was omitted from the method ofpreparation, and there was "obtained 25.0 per cent by volume of 400 F.end

point gasoline, and 4.5 per cent by weight of uncondensed gas.

8. Finely divided magnesium silicate prepared in accordance with Example5, supra, in which NH4NO3 was employed in the activating treatment, waspelleted in a conventional pelleting machine. The catalyst pellets wereintroduced into an externally heated reaction vessel, and a cent byweight and a per cubic foot.

The finely divided silicate, activated by treatment with NHANO3 asdescribed above, was pel-' leted in a conventional pelleting machine,and the catalyst pellets were introduced into an externally heatedreaction vessel. A petroleum gas oil having a distillation range of 282F. to 692 F. and an A. P. I. gravity of 33.1 was vaporized and passed atsubstantially atmospheric pressure through the vessel containing thecatalyst pellets. The reaction temperature was maintained at 890 F., andthe flow rate at 1.2 volumes of gas oil per volume of catalyst perhour.- The products of the cracking reaction were collected andseparated by fractionation and there was obpetroleum, gas oil having adistillation range of 282 F. to 692 F. and an A. P. I. gravity of 33.1was vaporized and passed at substantially atmospheric pressure throughthe reaction vessel containing the catalyst pellets. The reactiontemperature was maintained at 888 F., and the flow rate at 1 volume ofgas oil per volume 01 catalyst per hour. The products of the crackingreaction were collected and separated by-fractionation, and there wasobtained 31.4 per cent by volume of 400 F. end point gasoline and 5.9per cent by weight of uncondensed gas, based upon the oil initiallycharged. The cracking reaction was repeated, using magnesium silicateprepared'in the manner set forth in Example 5, with the exception that Ithe NHiNO: treatment was omitted, and

there was obtained 25.0 per cent by volume of 400 F. end point gasoline,and 4.5 per cent by weight of uncondensed gas.

9. Finely divided commercial magnesium silicate-activated by treatmentwith- NH4NO3 as described in Example 6, was pelleted in a conventionalpelleting machine, and the catalyst pellets were introduced into anexternally heated reaction vessel. A petroleum gas oil having adistillation range of 282 F. to 692 F. and an A. P. I. gravity of 33.1was vaporized and passed at substantially atmospheric pressure throughthe vessel containing the catalyst pellets. The reaction temperaturewas'm-aintained at 883 F., and the flow rate at 1.2 volumes of gas oilper volume of catalyst per hour. The products of the cracking reactionwere collected and separated by fractionation and there was obtained29.0 per cent by volume of 400 F. end point gasoline, and 8.0% by.weight of uncondensed gas, based upon the oil initially charged. Thecracking reaction was repeated, using magnesium silicate which had-notbeen subjected to an activiting treatment with NI'IANOIl, and there wasobtained 25.0 per cent by volume of 400 F. end point gasoline, and 4.0per cent by weight of uncondensed gas.

10. 220 parts by weight of a commercial .magnesium silicatecorresponding to the formula 2MgO.3Si02, having a volatile content of25.6 per cent by weight and a volume weight of 42.4 lbs, per cubic foot,was dispersed in 3000 parts by weight of water, and a solution of 160parts by weight of NHiNO': in 1000 parts by weight of water was added.The mixture was boiled for 2 hours with constant agitation, and theinsoluble silicate was filtered from the solution, thoroughly washedwith water, and dried. The activated silicate had a volatile content(water) or 23.2 per tained 32.6 per cent by volume of 400 F. end pointgasoline, and 9.8% by weight of uncondensed gas, based upon the oilinitially charged. The cracking reaction was repeated, using the initialsilicate which had not been subjected to an activating treatment withNHcNOs, and there was obtained 16.5 per cent by volume of 400 F. endpoint gasoline, and 3.9 per cent by weight of uncondensed gas.

The adsorbent and catalyst compositions of the present invention may beregenerated or revivined after their decolorizing or catalytic activity,has decreased through adsorption of carbonaceous materials during use,by treating such used adsorbents or catalysts with a solvent or solventmixture capable of dissolving or displacing the.

undesirable carbonaceous materials. For example, the used adsorbents orcatalyst may be washed with naphtha, alcohols, ketones, benzol,chlorinated hydrocarbon solvents, or mixtures thereof such as naphthaand acetone, in order to dissolve and remove adsorbed carbonaceousmaterials. Or, the used adsorbents or catalysts, with or withoutpreliminary washing or steaming, may be regenerated by heating,preferably in the presence of air, or gases containing controlledamounts of oxygen, in order to remove carbonaceous impurities.

I claim:

1. A-method of treating petroleum hydrocarbons, which comprisescontacting said hydrocarbons, at a temperature within the range of from700 F. to 1150 F., with a catalyst comprising a water-insolublemagnesium silicate activated by treatment with an ammonium compound inaqueous solution at a temperature between 150 F. and 400 F.

2. A method of treating petroleum hydrocarbons, which comprisescontacting said hydrocarbons at a temperature within the range of from700 F. to 1150 F., with a catalyst comprising a water-insolublemagnesium silicate formed by the reaction in aqueous solution of analkali metal silicate and a water-soluble salt of magnesium, in thepresence of a compound yielding NH4+ ions in aqueous solution at atemperature between 150 F. and 400 F., the insoluble silicate thereafterbeing washed with water to remove soluble salts, and d led.

3. A method of treating petroleum hydrocarbons, which comprisescontacting said hydrocarbons, at a temperature within the range of from700 F. to 1150 F., with a catalyst comprising a the reaction in aqueoussolution of sodium silicate and magnesium chloride, in the presence ofammonium chloride at a temperature between F. and 400 F., the insolublesilicate thereafter beins washed with water to remove soluble salts, anddried. I

4. A method of converting petroleum hydrocarbons into motor fuel, whichcomprises contacting said hydrocarbons, at a temperature within therange 01 from 850 F. to1050 F. with a catalyst comprising awater-insoluble magnesium silicate activated by treatment with anammonium compound temperature between 150 F. and 400 F.

5. A method of converting petroleum hydrocarbons into motor fuel, whichcomprises .contacting said hydrocarbons, at a temperature within therange of from 850 F. to 1050 F., with a catalyst comprising awater-insoluble magnesium silicate formed by the reaction in aqueoussolution of an alkali metal silicate and a watersoiuble salt ofmagnesium, in the presence of a compound yielding NA4+ ions in aqueoussolution at a temperature between 150 F. and 400 F., the insolublesilicate thereafter being washed with water to remove soluble salts, anddried.

WIIHAM A. LA LANDE, JR.

in aqueous solution at a 12 a aaraamcn's crrm The roilowing referencesare or record in the file of this patent:

5 UNITED STATES PATENTS Number Name Date 2,324,518 Klein July 20, 19482,337,684 Scheineman Dec. 28, 1043 10 2,355,388 Michael et ai A118. 8,1944 2,367,694 Snuggs Jan. 23, 1945 2,390,556 Ruthrui! Dec. 11, 10452,399,261 Thomas Apr. 30, 1946 2,402,804 Chichot Jan. 25, 1946 i5FOREIGN PATENTS Number Country Date 7 504,614 Great Britain Apr. 24.1988

